US4427758A - Single exposure positive-working photopolymer element - Google Patents

Single exposure positive-working photopolymer element Download PDF

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US4427758A
US4427758A US06/307,648 US30764881A US4427758A US 4427758 A US4427758 A US 4427758A US 30764881 A US30764881 A US 30764881A US 4427758 A US4427758 A US 4427758A
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layer
photopolymerizable
photopolymer element
gelatin
coated
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John A. Quinn
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EIDP Inc
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EI Du Pont de Nemours and Co
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Priority to US06/307,648 priority Critical patent/US4427758A/en
Assigned to E.I. DU PONT DE NEMOURS AND COMPANY, A CORP. OF DE. reassignment E.I. DU PONT DE NEMOURS AND COMPANY, A CORP. OF DE. ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: QUINN, JOHN A.
Priority to EP82304264A priority patent/EP0076565B1/en
Priority to DE8282304264T priority patent/DE3271152D1/de
Priority to JP57169930A priority patent/JPS5868741A/ja
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
    • G03F1/54—Absorbers, e.g. of opaque materials
    • G03F1/56—Organic absorbers, e.g. of photo-resists
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor

Definitions

  • This invention relates to a low cost, single exposure, aqueous processable, positive-working photopolymer element with excellent image quality suitable for use in electronic imaging, for example, and to a novel imaging process.
  • FIGS. 1-4 The invention is illustrated schematically in FIGS. 1-4.
  • FIG. 1 is a schematic cross-sectional view of the single exposure positive-working photopolymer element of the invention.
  • FIGS. 2 and 3 illustrate in section and schematically the exposure and development of the photopolymer element of FIG. 1.
  • FIG. 4 illustrates a schematic cross-section of a finished, direct positive image made by the exposure/development sequence of FIGS. 2-3.
  • a positive-working photopolymer element consisting essentially of a support, on one side of which is coated, in order, (1) a nonphotosensitive layer comprising a hardenable binder having a releasable hardening agent mixed therein, and (2) a permeable photopolymerizable layer.
  • the invention is directed to a single exposure positive-working dual layer photopolymer element consisting essentially of a support, an opaque, nonphotoactive layer comprising carbon black, gelatin and glutaraldehyde bisulfite (GDA-HSO 3 ) on said support, and a photopolymerizable layer coated contiguous thereto.
  • the photopolymer element After imagewise exposure of the photopolymerizable layer, the photopolymer element is treated with an aqueous developer solution containing K 2 CO 3 /KHCO 3 . This solution preferentially diffuses through the unexposed regions of the photopolymerizable layer to the opaque layer, releasing glutaraldehyde, which vary rapidly hardens the surrounding gelatin. The entire photopolymerizable layer and the unhardened portions of the opaque layer are then removed by washing, leaving a direct positive image of the original.
  • glutaraldehyde will very rapidly harden gelatin, particularly at high pH, but because of its volatility, mobility and reactivity, glutaraldehyde itself would be undesirable in a photographic system. However, it reacts with sodium bisulfite to form a stable, crystalline, water-soluble addition product. In the presence of carbonate, this reaction is reversed, liberating free glutaraldehyde.
  • the two-layer structure of the present invention with a photopolymerizable layer coated on top of a gelatin layer that contains glutaraldehyde-sodium bisulfite together with a colorant such as carbon black, is based on this reaction mechanism. But the same principle can be applied to analogous reactants, as will be further explained.
  • FIG. 1 shows the positive-working photopolymer element of this invention prior to exposure wherein support 1 is coated with nonphotosensitive layer 2 comprised of a hardenable binder containing a releasable hardening agent, and a top layer 3 which is the permeable photopolymerizable layer, i.e., the imaging layer.
  • nonphotosensitive layer 2 comprised of a hardenable binder containing a releasable hardening agent
  • top layer 3 which is the permeable photopolymerizable layer, i.e., the imaging layer.
  • the element is being exposed by actinic radiation 4 and 4a through an image 5.
  • Rays 4 are prevented from striking the photopolymerizable layer 3 while rays 4a strike said layer, causing photopolymerization in exposed areas 7.
  • Areas 6 are unexposed, and unpolymerized, and therefore remain permeable.
  • FIG. 3 shows development by contacting the exposed element with a developer liquid 9 which permeates through the unpolymerized areas 6 and causes the hardening agent in the underlying areas of layer 2 to be released, hardening the binder in those areas.
  • FIG. 4 shows the final, positive image obtained after wash-out of the unhardened areas of layer 2, with the simultaneous removal of all of layer 3, if desired.
  • the support 1 is CRONAR polyester, a trademark of E. I. du Pont de Nemours and Company, Wilmington, Del. for a flexible transparent polyethylene terephthalate film, which in this case is suitably subbed (subcoated);
  • the nonphotosensitive layer 2 is gelatin containing carbon black as a colorant for producing a visible image and glutaraldehyde-sodium bisulfite as the releasable hardener;
  • the permeable photopolymerizable layer 3 is the negative-working system described in Bratt et al, "Dot-Etchable Photopolymerizable Elements", U.S. Pat. No. 4,229,517, Example 1.
  • An optional cover sheet may be coated or laminated to photopolymerizable layer 3 to protect it and to prevent oxygen inhibition.
  • An imagewise exposure of this layer 3 to an exposure source rich in ultraviolet radiation will produce image areas 7 of polymerized material in the region struck by this radiation.
  • developer 9 e.g., aqueous Na 2 CO 3
  • these areas will act as a diffusion resist, i.e., will be slow to diffuse developing agent 9.
  • the unexposed and unpolymerized areas 6 will diffuse the developer rapidly into the underlying areas of layer 2, releasing the hardener in these areas and causing crosslinking of the gelatin.
  • the noncrosslinked areas can then be washed out with warm water, along with the imaging layer 3, leaving a colored, positive image on the support.
  • Suitable supports may be chosen from a wide variety of films composed of high polymers, e.g., polyamides, polyolefins, polyesters, vinyl polymers and cellulosic esters having a variety of thickeners. Also useful are metal foils, papers and the like. The choice of support is not vital to this invention although polyethylene terephthalate, suitably subbed to receive the nonphotosensitive layer, is preferred.
  • the nonphotosensitive layer is comprised of a hardenable binder which may be gelatin (preferred) or such materials as polyvinyl alcohol (PVA), carbamated PVA, polyacrylamide, polyethylene imine, carboxymethyl cellulose (CMC), hydroxyethyl cellulose (HEC) or mixtures with CMC, etc.
  • a hardenable binder which may be gelatin (preferred) or such materials as polyvinyl alcohol (PVA), carbamated PVA, polyacrylamide, polyethylene imine, carboxymethyl cellulose (CMC), hydroxyethyl cellulose (HEC) or mixtures with CMC, etc.
  • Releasable hardeners compatible with the hardenable binder must be selected.
  • glutaraldehyde-sodium bisulfite is particularly efficacious with gelatin and PVA as well as polyacrylamides and polyethylene imine.
  • hardeners of gelatin include, for example, glyoxal-sodium bisulfite, formaldehyde-sodium bisulfite, and starch dialdehyde-sodium bisulfite (or other alkali metal salts of the above).
  • the organic titanates sold by E. I. du Pont de Nemours and Company, Wilmington, DE as TYZOR, for example, can be used as releasable hardeners for CMC as can the salts of Cr +3 .
  • aqueous alkalis such as Na 2 CO 3 (sodium carbonate), KOH, NaOH, etc.
  • Other adjuvants may be present to help wash out the unhardened portion of this layer and to assist in finally removing all the image-forming photopolymerizable layer if desired.
  • colorants i.e., pigments and dyes
  • pigments and dyes may be added to the nonphotosensitive layer to provide image coloring if desired.
  • Carbon black colloidal carbon
  • other materials such as iron oxide may also be used effectively. They must be compatible with the hardenable binder, however.
  • ultraviolet dyes examples include ultraviolet dyes, ultraviolet absorbers, and other dyes which can be used in this invention.
  • Photopolymerizable compositions the molecular weight of at least one component of the composition is increased by exposure to actinic radiation, causing a change in the rheological and thermal properties of the exposed areas and rendering the exposed areas relatively less soluble in solvents than the unexposed areas, thereby producing a solvent-developable image.
  • Photopolymerizable compositions for use in the invention usually comprise a photoinitiator, an actinic radiation absorber to opacify layer 2 in the actinic region of the spectrum, a photopolymerizable monomer, and a polymeric binder, as described further below.
  • the photopolymerizable composition contains an organic, free-radical generating system activatable by actinic radiation, i.e., 300 nm and above, which initiates polymerization of the ethylenically unsaturated compound and does not subsequently terminate the reaction.
  • the free-radical generating system should have at least one component that has an active radiation absorption band with a molar extinction coefficient of at least about 50 within the range of about 300 to 500 nm.
  • Active radiation absorption band means a band of radiation which is active to produce the free radical necessary to initiate the polymerization.
  • the free-radical generating system can comprise one or more compounds which directly furnish free radicals when activated by radiation. It can also comprise a plurality of compounds, one of which yields free radicals after having been caused to do so by a sensitizer which is activated by the radiation.
  • Photoinitiators which can be utilized in the practice of this invention include aromatic ketones such as benzophenone, Michler's ketone (4,4'-bis(dimethylamino)benzophenone), 4,4'-bis(diethylamino)benzophenone, 4-methoxy-4'-dimethylamino-benzophenone, 2-ethylanthraquinone, phenathraquinone, and other aromatic ketones; benzoin, benzoin esters such as benzoin methyl ether, benzoin ethyl ether and benzoin phenyl ether, methylbenzoin, ethylbenzoin and other benzoins; and 2,4,5-triarylimidazole dimers such as 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-(m-methoxyphenyl)imidazole dimer, 2-(o-flu
  • Particularly useful initiators are the 2,4,5-triarylimidazole dimers (also known as hexaarylbiimidazoles). These are used with a free-radical producing electron donor agent, such as 2-mercaptobenzoxazole, leuco crystal violet or tri(4-diethylamino-2-methylphenyl)-methane. Such sensitizers as Michler's ketone may be added. Various energy transfer dyes, such as Rose Bengal and Eosin Y, can also be used. Additional examples of suitable initiators are disclosed in U.S. Pat. No. 2,760,863.
  • the free-radical generating system is employed in a concentration sufficient to initiate polymerization, which is usually about 0.1-25% by weight based on total composition, and preferably about 2 to 20% by weight.
  • the instant invention is not limited to the use of any particular polymerizable monomer, it being required only that the monomer be ethylenically unsaturated and capable of addition polymerization.
  • a large number of useful monomers is available, generally characterized by one or more terminal ethylenic groups.
  • suitable monomers may be mentioned various vinyl and vinylidene monomers, e.g., vinyl carboxylates, alpha-alkyl acrylates, alpha-substituted acrylic acids and esters thereof, vinyl ester, vinyl hydrocarbons, acrylic and alpha-substituted acrylic acid esters of the polymethylene glycols and ether alcohols, all as disclosed in U.S. Pat. No.
  • the concentration of the monomer or monomers employed is normally about 7.5-35% by weight based on the total solids of the composition, and preferably between 15-25%.
  • the binder used in the photopolymer layer is an organic polymeric material that is preferably solid at 50° C., and it is necessary that the binder be compatible with the polymerizable monomer and the polymerization initiator system. It is frequently desirable, but it is not required, that the binder be thermoplastic.
  • the binder may be of the same general type as the polymerizable monomer being used and may be soluble therein and plasticized thereby.
  • binders both thermoplastic and nonthermoplastic
  • binders both thermoplastic and nonthermoplastic
  • U.S. Pat. No. 3,060,023 e.g., cellulose ethers or esters; polyalkylene ethers; condensation polymers of glycols with dibasic acids; polymers and copolymers of vinyl esters; acrylic acids and esters; polyvinyl alcohol; cellulose; phenolic resins; and the like.
  • Other binders including a number of vinylidene polymers are disclosed in U.S. Pat. Nos. 2,760,863 and 2,791,504.
  • Still other useful binders are the N-methoxymethyl polyhexamethylene adipamide mixtures of British Pat. No.
  • the binder or binder mixture usually comprises 10-75% by weight of the total solids.
  • binders are acidic, polymeric, organic compounds since the photopolymerizable composition resulting is developable in an aqueous alkaline solvent devoid of organic solvents. This is advantageous since organic solvents are costly, may be hazardous with respect to toxicity and/or flammability, may become scarce due to petrochemical shortages, and may pollute the air and water.
  • One class of film-forming binders which is soluble in aqueous alkaline media and is useful in the compositions of the present invention is made up of vinyl addition polymers containing free carboxylic acid groups, which are prepared from 30 to 94 mole percent of one or more alkyl acrylates and 70 to 6 mole percent of one or more alpha-beta-ethylenically unsaturated carboxylic acids, and more preferably prepared from 61 to 94 mole percent of two alkyl acrylates and 39 to 6 mole percent of an alpha-beta-ethylenically unsaturated carboxylic acid.
  • Suitable alkyl acrylates for use in preparing these polymeric binders include methyl acrylate, ethyl, acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, etc.
  • Suitable alpha-beta-ethylenically unsaturated carboxylic acids include acrylic acid, methacrylic acid and the like. Binders of this type, including their preparation, are described in German OLS No. 2,320,849 (published 1973).
  • acidic binders can also be obtained by selecting a preformed, compatible macromolecular polymeric binding agent which is a copolymer of (1) a styrene-type of a vinyl monomer and (2) an unsaturated carboxy-containing monomer, as described in detail in British Pat. No. 1,361,298.
  • Another preferred photopolymerizable composition is obtained by using a preformed, compatible macromolecular polymeric binding agent mixture, the components thereof taken from two selected classes.
  • the first type is preferably selected from a copolymer of vinyl acetate and crotonic acid; a terpolymer of ethyl acrylate, methyl methacrylate, and acrylic acid; and cellulose acetate succinate.
  • the second type is preferably selected from toluene sulfonamide formaldehyde; a copolymer of methyl methacrylate and methacrylic acid; a terpolymer of methyl methacrylate, ethyl acrylate, and hydrogen maleate; a terpolymer of vinyl chloride, vinyl acetate, and maleic acid; a copolymer of styrene and maleic anhydride; and a terpolymer of methyl methacrylate, ethyl acrylate, and methacrylic acid.
  • the nonphotosensitive layer may be coated on the support from an appropriate solvent (e.g. water). After drying, the photopolymerizable layer is applied from its appropriate solvent.
  • a cover sheet e.g., a thin polyethylene terephthalate sheet sold as MYLAR polyester, a trademark of E. I. du Pont de Nemours and Company, is usually laminated over the photopolymerizable layer.
  • Example 1 is considered to be the best mode:
  • This composite product is exposed through the cover sheet and a negative test image for about 10 seconds to a 4 kw xenon light source at a distance of 60 inches.
  • the cover sheet is then stripped from the exposed element and processed in a solution comprising 840 g. K 2 CO and 50 g. KHCO 3 in 16 liters of distilled water.
  • the developing solution diffuses rapidly through the nonimaged areas of the photopolymer film 3 into the corresponding areas of the black, nonphotosensitive layer 2 underneath.
  • the glutaraldehyde is released in these areas, causing the gelatin to crosslink and harden.
  • Example 2 This composition is coated on sample layer 2 made according to the instructions of Example 1 which had been coated on a polyethylene terephthalate film support as taught therein.
  • a Mylar polyester cover sheet is then laminated over the photopolymerizable layer and an exposure similar to that described in Example 1 is given to this element. The cover is then removed and the image developed as in Example 1.
  • a high quality, direct positive image is obtained with excellent density and dot quality.
  • This example demonstrates the use of yet another photopolymerizable layer in conjunction with the nonphotosensitive, hardenable layer of this invention.
  • This composition is coated on a film support and overcoated with the photopolymerizable composition of Example 1.
  • a cover layer is applied and the element is exposed and developed as described in Example 1.
  • An excellent, positive image is obtained which indicates that glyoxal-sodium bisulfite can be used as the releasable hardener in this invention.
  • Example 1 This is coated on a support, overcoated with a photopolymerizable layer, laminated with a cover sheet, exposed and developed as described in Example 1.
  • a fine, high quality direct positive image is obtained which demonstrates that polyvinyl alcohol binder and boric acid as the releasable hardener can be used within the metes and bonds of this invention.
  • This material is coated on a polyethylene terephthalate film support as described in Example 1.
  • This composition is overcoated on layer 2 made above, using a 2 mil doctor knife, and dried.
  • a polyethylene terephthalate cover sheet is laminated over this structure.
  • the photopolymer element is exposed and developed as described in Example 1. A high quality, dark violet, direct positive image is obtained.
  • This composition is coated on a copper surface of a copper/epoxy laminate board and dried.
  • the photopolymerizable composition from Example 5 is applied over this layer, dried and a conventional cover sheet applied thereon.
  • the composition element is exposed and developed as described in Example 1. A yellow positive image on the copper layer is obtained.
  • the image is then etched with 39° Baume ferric chloride at 130° F. to remove the copper in the nonimage area, showing that properly used, this element will function as a photoresist.
  • This material is coated on a support as described in Example 1 and dried.
  • a photopolymerizable layer made as described in Example 1 is coated over this layer, dried and a conventional cover sheet applied thereon.
  • This composite structure is exposed and developed as described in Example 1. An excellent, high quality direct positive image with good density and dot quality is achieved.
  • another sample of the composite described in this example is exposed and simply processed by dipping for 25 seconds in a 1% KOH solution at 75° F. and rinsed under 100° F. water. The resulting product was a superior direct positive image with high density and excellent dot quality.
  • Example 1 This material is coated on a suitable support as described in Example 1.
  • a photopolymerizable layer made according to Example 1 is applied over this dried layer and a conventional cover sheet laminated thereon.
  • the composite product is exposed as described in Example 1 and developed by washing in 5% alcoholic KOH at 75° F. and 100° F. water washing. A suitable direct positive image is obtained.
  • This material is coated on a support, dried, a photopolymerizable layer applied thereon, followed by drying and lamination of a cover sheet all as described in Example 1.
  • the composite product is exposed as described in Example 1 followed by development in 5% alcoholic KOH and water washing at 100° F. A suitable direct positive image is obtained.
  • Example 1 This is coated on a support, dried, overcoated with photopolymerizable composition, dried, and a cover sheet laminated thereto as described in Example 1.
  • the composite product is exposed as described in Example 1 and developed by 5% alcoholic KOH (2 mins. at 75° F.) and water washing in 100° F. water. A suitable direct positive image is obtained.
  • Example 1 This is coated on a support, dried, overcoated with photopolymerizable solution, dried, and a cover sheet laminated thereto as described in Example 1.
  • the composite product is exposed as described in Example 1 and developed by 5% alcoholic KOH at 75° F. followed by washing in water at 100° F. A suitable direct positive image is obtained.

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  • Engineering & Computer Science (AREA)
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US06/307,648 1981-10-01 1981-10-01 Single exposure positive-working photopolymer element Expired - Lifetime US4427758A (en)

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US06/307,648 US4427758A (en) 1981-10-01 1981-10-01 Single exposure positive-working photopolymer element
EP82304264A EP0076565B1 (en) 1981-10-01 1982-08-12 Single exposure positive-working photopolymer element
DE8282304264T DE3271152D1 (en) 1981-10-01 1982-08-12 Single exposure positive-working photopolymer element
JP57169930A JPS5868741A (ja) 1981-10-01 1982-09-30 光重合体エレメント

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Cited By (7)

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US5599616A (en) * 1994-11-30 1997-02-04 Polaroid Corporation Laminar imaging medium utilizing cross-linked borated polymeric binder
US20040161769A1 (en) * 2002-09-06 2004-08-19 The Procter & Gamble Company Microbial oxidoreductase
US20050053870A1 (en) * 2003-09-05 2005-03-10 Willard Randall Orson Leuco dye-containing coating compositions
US20050064324A1 (en) * 2003-09-22 2005-03-24 Eastman Kodak Company Thermal imaging composition and member and methods of imaging and printing
US20060093958A1 (en) * 2004-10-28 2006-05-04 Vladek Kasperchik Color forming compositions and associated methods
US20060147833A1 (en) * 2003-01-24 2006-07-06 Kasperchik Vladek P Color forming compositions with improved marking sensitivity and image contrast and associated methods
US20070269737A1 (en) * 2006-05-16 2007-11-22 Bhatt Jayprakash C Color forming compositions and associated methods

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DE3581671D1 (de) * 1984-07-25 1991-03-14 Hoechst Japan K K Verfahren und material zur herstellung mehrfarbiger reproduktionen.
JPS63133153A (ja) * 1986-11-26 1988-06-04 Fuji Photo Film Co Ltd 湿し水不要感光性平版印刷版
JPH0782235B2 (ja) * 1988-05-09 1995-09-06 富士写真フイルム株式会社 画像形成材料
JPH0782234B2 (ja) * 1988-05-09 1995-09-06 富士写真フイルム株式会社 画像形成材料
JPH02960A (ja) * 1988-05-31 1990-01-05 Somar Corp 遮光性マスキングフィルム
JPH0675373A (ja) * 1992-08-28 1994-03-18 Toppan Printing Co Ltd 感光性着色組成物およびカラーフィルターの製造方法およびカラーフィルター
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US4268601A (en) 1977-07-15 1981-05-19 Fuji Photo Film Co., Ltd. Photosensitive image forming material and an image forming method using same

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5599616A (en) * 1994-11-30 1997-02-04 Polaroid Corporation Laminar imaging medium utilizing cross-linked borated polymeric binder
US20040161769A1 (en) * 2002-09-06 2004-08-19 The Procter & Gamble Company Microbial oxidoreductase
US20060147833A1 (en) * 2003-01-24 2006-07-06 Kasperchik Vladek P Color forming compositions with improved marking sensitivity and image contrast and associated methods
US20070281244A9 (en) * 2003-01-24 2007-12-06 Kasperchik Vladek P Color forming compositions with improved marking sensitivity and image contrast and associated methods
US7700258B2 (en) 2003-01-24 2010-04-20 Hewlett-Packard Development Company, L.P. Color forming compositions with improved marking sensitivity and image contrast and associated methods
US20050053870A1 (en) * 2003-09-05 2005-03-10 Willard Randall Orson Leuco dye-containing coating compositions
US7462443B2 (en) 2003-09-05 2008-12-09 Hewlett-Packard Development Company, L.P. Leuco dye-containing coating compositions
US20050064324A1 (en) * 2003-09-22 2005-03-24 Eastman Kodak Company Thermal imaging composition and member and methods of imaging and printing
US7022461B2 (en) * 2003-09-22 2006-04-04 Eastman Kodak Company Thermal imaging composition and member and methods of imaging and printing
US20060093958A1 (en) * 2004-10-28 2006-05-04 Vladek Kasperchik Color forming compositions and associated methods
US20070269737A1 (en) * 2006-05-16 2007-11-22 Bhatt Jayprakash C Color forming compositions and associated methods
US8283100B2 (en) 2006-05-16 2012-10-09 Hewlett-Packard Development Company, L.P. Color forming compositions and associated methods

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EP0076565A1 (en) 1983-04-13
JPH0150892B2 (enrdf_load_stackoverflow) 1989-11-01
EP0076565B1 (en) 1986-05-14
DE3271152D1 (en) 1986-06-19
JPS5868741A (ja) 1983-04-23

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